Silver cluster-assembled materials (SCAMs), by virtue of their tunable structure, accessible surface area and excellent stability, hold great promise as highly efficient catalysts. Herein, we report a new SCAM [Ag12(S t Bu)6(CF3COO)3(TPyP)] n (denoted as Ag12TPyP) composed of a Ag12 chalcogenolate cluster core stabilized by porphyrinic ligands. Ag12TPyP showed superior sulfur mustard simulant (2-chloroethyl ethyl sulfide, CEES) degradation efficiency and achieved a half lifetime (t 1/2) of 1.5 min with 100% selectivity. The experimental results demonstrated that synergistic effects between the silver cluster and photosensitizer ligand promote the efficiency of the generation of singlet oxygen (1O2), which accelerates the decontamination rate. Additionally, benefiting from strong affinity between the silver cluster and CEES, Ag12TPyP exhibits a CEES uptake of 74.2 mg g–1. This work demonstrates that SCAMs offer a new route to the rational design of novel materials for the detoxification of mustard gas.

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The usage of ZnO as active layers to fabricate hybrid heterojunction light-emitting diodes is expected to be an effective approach for ultraviolet light sources. Individual ZnO microwires with controlled gallium (Ga) incorporation (ZnO/Ga MWs) have been fabricated via a chemical vapor deposition method. It is found that with the increasing Ga-incorporated concentration, the near-band-edge (NBE) photoluminescence of the ZnO MWs blue-shifted gradually from 390 to 370 nm. Heterojunction diodes comprising single ZnO/Ga MWs and p-GaN have been fabricated. With increasing injection currents, the interfacial emissions can be suppressed effectively and the typical NBE emission dominates the electroluminescence (EL). In particular, with increasing Ga-doping concentration, the dominant EL emission wavelengths of the ZnO/Ga MW-based heterojunction diodes blue-shifted from 384 to 372 nm, and the blue shift can be ascribed to the Burstein-Moss effect induced by the Ga incorporation. The present work demonstrates the feasibility of optical band gap engineering of ZnO MWs and the potential application for wavelength-tuning ultraviolet light sources.

Deciphering the precise physical mechanism of interaction between an adsorbed species and a reactive site in heterogeneous catalysis is crucial for predictive design of highly efficient catalysts. Here, using first-principles calculations we identify that the two-dimensional ferromagnetic metal organic framework of Mn 2 C 18 H 12 can serve as a highly efficient single-atom catalyst for spin-triplet O 2 activation and CO oxidation. The underlying mechanism is via "concerted charge-spin catalysis", involving a delicate synergetic process of charge transfer, provided by the hosting Mn atom, and spin selection, preserved through active participation of its nearest neighboring Mn atoms for the crucial step of O 2 activation. The synergetic mechanism is further found to be broadly applicable in O 2 adsorption on magnetic X 2 C 18 H 12 (X = Mn, Fe, Co, and Ni) with a well-defined linear scaling dependence between the chemical activity and spin excitation energy. The present findings provide new insights into chemical reactions wherein spin selection plays a vital role.

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